Note: Descriptions are shown in the official language in which they were submitted.
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DRYER-ACTIVATED FABRIC CONDITIONING COMPOSITIONS
CONTAINING ETHOXYLATED/PROPOXYLATED SUGAR DERIVATIVES
TECHNICAL FIELD
S The present invention relates to an improvement in dryer activated, e.g.,
dryer-
added, softening products, compositions, and/or the process of making these
compositions. These products and/or compositions are either in particulate
form,
compounded with other materials in solid form, e.g. tablets, pellets,
agglomerates,
etc., or, preferably, attached to a substrate.
SUMMARY OF THE INVENTION
The present invention relates to dryer-activated fabric softening compositions
and articles comprising:
(A) at least about 5% of highly alkoxylated sugar derivative containing a
sugar moiety, at least about S ethylene oxide, propylene oxide, or
mixtures thereof, groups per molecule and at least one long
hydrophobic moiety containing from about 8 to about 30 carbon atoms
per molecule; and
(B) from 10% to about 95% of a co-softener comprising a carboxylic acid
sale of a tertiary amine.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to fabric softening compositions and articles
having improved antistatic effects, for use in an automatic clothes dryer.
These
compositions comprise, as ingredients:
(A) at least about 5%, preferably from about 10% to about 90%, more
preferably from about 10% to about 75%, and even more preferably
from about 15% to about 55%, of highly ethoxylated and/or
propoxylated, preferably at least S EO or PO groups per molecule,
more preferably at least about 10, and even more preferably 15, EO
groups per molecule, sugar derivative containing at least one long
hydrophobic moiety per molecule; and, preferably,
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(B) from 0% to about 95%, preferably from about 10% to about 75%,
more preferably from about 20% to about 60%, of a carboxylic acid
salt of a tertiary amine.
The active components can contain unsaturation for additional antistatic
benefits. The components are selected so that the resulting fabric treatment
composition has a melting point above about 38°C and is flowable at
dryer operating
temperatures.
(A) The Ethoxylated/Propoxylated Sugar Derivative
The ethoxylated and/or propoxylated sugar derivative contains a "sugar"
moiety, e.g., a moiety derived from, e.g., a polyhydroxy sugar, or sugar
alcohol, that
contains from about 4 to about 12 hydroxy groups. This sugar moiety is
substituted
by at least one long hydrophobic group, containing from about 8 to about 30
carbon
atoms, preferably from about 16 to about 18 carbon atoms. For improved
physical
characteristics, e.g., higher melting point, the hydrophobic group can contain
more
carbon atoms, e.g., 20-22, and/or there can be more than one hydrophobic
group,
preferably two or, less preferably, three. In general, it is preferred that
the
hydrophobic group is supplied by esterifying one of the hydroxy groups with a
fatty
acid. However, the hydrophobic group can be supplied by esterifying the
hydroxy
group to connect the hydrophobic group to the sugar moiety by an ether
linkage,
and/or a moiety containing a carboxy group esterified with a fatty alcohol can
be
attached to the sugar moiety to provide the desired hydrophobic group.
Sugar moieties include sucrose, galactose, mannose, glucose, fructose,
sorbitan, sorbitol, mannitol, inositol, etc., and/or their derivatives such as
glucosides,
galactosides, etc. Other "sugar" types of moieties containing multiple hydroxy
groups can also be used including starch fractions and polymers such as
polyglycerols. The sugar moiety is any polyhydroxy group that provides the
requisite
number of hydroxy groups.
The hydrophobic group can be provided by attachment with an ester, ether, or
other linkage that provides a stable compound. The hydrophobic group is
preferably
primarily straight chain, and preferably contains some unsaturation to provide
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additional antistatic benefits. Such hydrophobic groups and their sources are
well
known, and are described hereinafter with respect to the more conventional
types of
softening agents.
The polyalkoxy chain can be all ethoxy groups, and/or can contain other
S groups such as propoxy, glyceryl ether, etc., groups. In general, polyethoxy
groups
are preferred, but for improved properties such as biodegradability, glyceryl
ether
groups can be inserted. Typically there are from about 5 to about 100,
preferably
from about 10 to about 40, more preferably from about 15 to about 30, ethoxy
groups,
or their equivalents, per molecule.
An empirical formula is as follows:
~"- (SUg~') (R'0)n
Wherein R is a hydrophobic group containing from about 8 to about 30,
preferably
from about 12 to about 22, more preferably from about 16 to about 18 carbon
atoms;
"sugar" refers to a polyhydroxy group, preferably derived from a sugar, sugar
alcohol,
1 S or similar polyhydroxy compound; R' is an alkylene group, preferably
ethylene or
propylene, more preferably ethylene; m is a number from 1 to about 4,
preferably 2;
and n is a number from about S to about 100, preferably from 10 to about 40. A
preferred compound of this type is polyethoxylated sorbitan monostearate,
e.g.,
Glycosperse S-20 from Lonza, which contains about 20 ethoxylate moieties per
molecule.
The level of the polyethoxy sugar derivative is typically at least about 5%,
preferably at least about 10%, more preferably at least about 15%. Preferably
the
maximum level is no more than about 90%, more preferably no more than about
75%.
The polyethoxy sugar derivative provides improved antistatic properties to the
compositions and can provide equivalent antistatic properties to conventional
dryer-
added compositions, and/or articles, even with less, or no, quaternary
ammonium
softener materials present. It is possible to prepare a dryer-added
composition, or
article, that is entirely non-ionic.
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(B) Co-Softener
Fabric softening compositions employed herein contain, as a preferred
component, at a level of from about 10% to about 95%, preferably from about
20% to
about 75%, more preferably from about 20% to about 60%, carboxylic acid salt
of a
tertiary amine which has the formula:
RS - N (R6) (R') - H(+)( ) 0 -C(0) - R8
wherein RS is a long chain aliphatic group containing from about 8 to about 30
carbon
atoms; R6 and R' are the same or different from each other and are selected
from the
group consisting of aliphatic groups containing from about 1 to about 30
carbon
atoms, hydroxyalkyl groups of the Formula R40H wherein R4 is an alkylene group
of
from about 2 to about 30 carbon atoms, and alkyl ether groups of the formula
R90(C"HZ"0)m wherein R9 is alkyl and alkenyl of from about 1 to about 30
carbon
atoms and hydrogen, n is 2 or 3, and m is from about 1 to about 30, and
wherein R8 is
selected from the group consisting of unsubstituted alkyl, alkenyl, aryl,
alkaryl and
aralkyl of about 1 to about 30 carbon atoms, and substituted alkyl, alkenyl,
aryl,
alkaryl, and aralkyl of from about 1 to about 30 carbon atoms wherein the
substituents are selected from the group consisting of halogen, carboxyl, and
hydroxyl, said composition having a melting point of from about 35°C to
about
100°C. All of the above alkyl groups can be interrupted by ether,
ester, and/or amide
linking moieties.
This component can provide the following benefits: superior odor, a decrease
in paint softening of the dryer drum, and/or improved fabric softening
performance,
compared to similar articles without this component. Either R5, R6, R', and/or
Rg
chains can contain unsaturation for improved antistatic benefits.
Tertiary amine salts of carboxylic acids have superior chemical stability,
compared to primary and secondary amine carboxylate salts. For example,
primary
and secondary amine carboxylates tend to form amides when heated, e.g., during
processing or use in the dryer. Also, they absorb carbon dioxide, thereby
forming
high melting carbamates which build up as an undesirable residue on treated
fabrics.
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Preferably, RS is an aliphatic chain containing from about 12 to about 30
carbon atoms, R6 is an aliphatic chain of from about 1 to about 30 carbon
atoms, and
R' is an aliphatic chain of about 1 to about 30 carbon atoms. Particularly
preferred
tertiary amines for static control performance are those containing
unsaturation; e.g.,
oleyldimethylamine and/or soft tallowdimethylamine.
Examples of preferred tertiary amines as starting material for the reaction
between the amine and carboxylic acid to form the tertiary amine salts are:
lauryldimethylamine, myristyldimethylamine, stearyldimethylamine,
tallowdimethylamine, coconutdimethylamine, dilaurylmethylamine,
distearylmethylamine, ditallowmethylamine, oleyldimethylamine, dioleyl
methylamine, lauryldi(3-hydroxypropyl)amine, stearyldi(2-hydroxyethyl)amine,
trilaurylamine, laurylethylmethylamine, and C,gH3,N[(OCZH4),oOH]2.
Preferred fatty acids are those wherein R8 is a long chain, unsubstituted
alkyl
or alkenyl group of from about 8 to about 30 carbon atoms, more preferably
from
about 11 to about 17 carbon atoms. Examples of specific carboxylic acids as a
starting material are: formic acid, acetic acid, lauric acid, myristic acid,
palmitic acid,
stearic acid, oleic acid, oxalic acid, adipic acid, 12-hydroxy stearic acid,
benzoic acid,
4-hydroxybenzoic acid, 3-chloro benzoic acid, 4-nitro benzoic acid, 4-ethyl
benzoic
acid, 4-(2-chloroethyl) benzoic acid, phenylacetic acid, (4-chlorophenyl)
acetic acid,
(4-hydroxyphenyl) acetic acid, and phthalic acid.
Preferred carboxylic acids are stearic, oleic, lauric, myristic, palmitic, and
mixtures thereof.
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The amine salt can be formed by a simple addition reaction,
well known in the art, disclosed in U.S. Pat. No. 4,237,155,
Kardouche, issued Dec. 2, 1980. Excessive levels of free amines
may result in odor problems, and generally free amines provide
poorer softening performance than the amine salts.
Preferred amine salts for use herein are those wherein the
amine moiety is a C8-C3p alkyl or alkenyl dimethyl amine or a
di-Cg-C30 alkyl or alkenyl methyl amine, and the acid moiety is a
Cg-C30 alkyl or alkenyl monocarboxylic acid. The amine and the
acid, respectively, used to form the amine salt will often be of
mixed chain lengths rather than single chain lengths, since these
materials are normally derived from natural fats and oils, or
synthetic processed which produce a mixture of chain lengths.
Also, it is often desirable to utilize mixtures of different chain
lengths in order to modify the physical or performance character-
istics of the softening composition.
Specific preferred amine salts for use in the present inven-
tion are oleyldimethylamine stearate, stearyldimethylamine stear-
ate, stearyldimethylamine myristate, stearyldimethylamine palmi-
fate, distearylmethylamine palmitate, distearylmethylamine laur-
ate, and mixtures thereof. A particularly preferred mixture is
oleyldimethylamine stearate and distearylmethylamine myristate, in
a ratio of 1:10 to 10:1, preferably about 1:1.
(C) ytional Inqredients
Well known optional components included in fabric condition-
ing compositions ire narrated in U.S. Pat. No. 4,103,047, Zaki et
al., issued July 25, 1978, for 'Fabric Treatment Compositions '.
(1) Optional Nonionic Softener
A highly preferred optional ingredient is a nonionic fabric
softening agent/material. Typically, such nonionic fabric
softener maters al s have an HLB of from about 2 to about 9, more
typically from about 3 to about 7. In general, the materials
selected should be relatively crystalline, higher melting, (e. g.,
>25'C).
D
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The level of optional non-ionic softener in the solid composition is typically
from about 10% to about 50%, preferably from about 15% to about 40%.
Preferred non-ionic softeners are fatty acid partial esters of polyhydric
alcohols, or anhydrides thereof, wherein the alcohol, or anhydride, contains
from
about 2 to about 18, preferably from about 2 to about 8, carbon atoms, and
each fatty
acid moiety contains from about 8 to about 30, preferably from about 16 to
about 20,
carbon atoms. Typically, such softeners contain from about one to about 3,
preferably
about 2 fatty acid groups per molecule.
The polyhydric alcohol portion of the ester can be ethylene glycol, glycerol,
poly (e.g., di-, tri-, tetra, penta-, and/or hexa-) glycerol, xylitol,
sucrose, erythritol,
pentaerythritol, sorbitol or sorbitan. These non-ionic fabric softening
materials do not
include the ethoxylated sugar derivatives disclosed hereinbefore. They
typically
contain no more than about 4 ethoxy groups per molecule.
The fatty acid portion of the ester is normally derived from fatty acids
having
from about 8 to about 30, preferably from about 16 to about 20, carbon atoms.
Typical examples of said fatty acids being lauric acid, myristic acid,
palmitic acid,
stearic acid, oleic acid, and behenic acid.
Highly preferred optional non-ionic softening agents for use in the present
invention are C,o Cz6 acyl sorbitan esters and polyglycerol monostearate.
Sorbitan
esters are esterified dehydration products of sorbitol. The preferred sorbitan
ester
comprises a member selected from the group consisting of C,o Cz6 acyl sorbitan
monoesters and C,o Cz6 acyl sorbitan diesters and ethoxylates of said esters
wherein
one of more of the unesterified hydroxyl groups in said esters contain from 1
to about
4 oxyethylene units, and mixtures thereof. For the purpose of the present
invention,
sorbitan esters containing unsaturation (e.g., sorbitan monooleate) are
preferred.
Sorbitol, which is typically prepared by the catalytic hydrogenation of
glucose, can be dehydrated in well known fashion to form mixtures of 1,4- and
1,5-
sorbitol anhydrides and small amounts of isosorbides. (See U.S. Pat. No.
2,322,821,
Brown, issued June 29, 1943.)
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The foregoing types of complex mixtures of anhydrides of sorbitol are
collectively referred to herein as "sorbitan". It will be recognized that this
"sorbitan"
mixture will also contain some free, uncyclized sorbitol.
The preferred sorbitan softening agents of the type employed herein can be
prepared by esterifying the "sorbitan" mixture with a fatty acyl group in
standard
fashion, e.g., by reaction with a fatty acid halide, fatty acid ester, and/or
fatty acid.
The esterification reaction can occur at any of the available hydroxyl groups,
and
various mono-, di-, etc., esters can be prepared. In fact, mixtures of mono-,
di-, tri-,
etc., esters almost always result from such reactions, and the stoichiometric
ratios of
the reactants can be simply adjusted to favor the desired reaction product.
For commercial production of the sorbitan ester material, etherification and
esterification are generally accomplished in the same processing step by
reacting
sorbitol directly with fatty acids. Such a method of sorbitan ester
preparation is
described more fully in MacDonald; "Emulsifiers:" Processing and Quality
Control:,
Journal of the American Oil Chemists' Society, Vol. 45, October 1968.
Details, including formula, of the preferred sorbitan esters can be found in
U.S. Pat. No. 4,128,484.
For the purposes of the present invention, it is preferred that a significant
amount of di- and tri- sorbitan esters are present in the ester mixture. Ester
mixtures
having from 20-50% mono-ester, 25-50% di-ester and 10-35% of tri- and tetra-
esters
are preferred.
The material which is sold commercially as sorbitan monoester (e.g.,
monostearate) does in fact contain significant amounts of di- and tri-esters
and a
typical analysis of commercial sorbitan monostearate indicates that it
comprises about
27% mono-, 32% di- and 30% tri- and tetra-esters. Commercial sorbitan
monostearate therefore is a preferred material. Mixtures of sorbitan stearate
and
sorbitan palmitate having stearate/palmitate weight ratios varying between
10:1 and
1:10, and 1,5-sorbitan esters are useful. Both the 1,4- and 1,5-sorbitan
esters are
useful herein.
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Other useful alkyl sorbitan esters for use in the softening compositions
herein
include sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate,
sorbitan monobehenate, sorbitan monooleate, sorbitan dilaurate, sorbitan
dimyristate,
sorbitan dipalmitate, sorbitan distearate, sorbiton dibehanate, sorbitan
dioleate, and
mixtures thereof, and mixed tallowalkyl sorbitan mono- and di-esters. Such
mixtures
are readily prepared by reacting the foregoing hydroxy-substituted sorbitans,
particularly the 1,4- and 1,5-sorbitans, with the corresponding acid or acid
chloride in
a simple esterification reaction. It is to be recognized, of course, that
commercial
materials prepared in this manner will comprise mixtures usually containing
minor
proportions of uncyclized sorbitol, fatty acids, polymers, isosorbide
structures, and
the like. In the present invention, it is preferred that such impurities are
present at as
low a level as possible.
The preferred sorbitan esters employed herein can contain up to about 15% by
weight of esters of the CZO Cz6, and higher, fatty acids, as well as minor
amounts of
Cg, and lower, fatty esters.
Glycerol and polyglycerol esters, especially glycerol, diglycerol,
triglycerol,
and polyglycerol mono- and/or di- esters, preferably mono-, are also preferred
herein
(e.g., polyglycerol monostearate with a trade name of Radiasurf 7248).
Glycerol
esters can be prepared from naturally occurring triglycerides by normal
extraction,
purification and/or interesterification processes or by esterification
processes of the
type set forth hereinbefore for sorbitan esters. Partial esters of glycerin
can also be
ethoxylated with no more than about 4 ethoxy groups per molecule to form
usable
derivatives that are included within the term "glycerol esters."
Useful glycerol and polyglycerol esters include mono-esters with stearic,
oleic, palinitic, lauric, isostearic, myristic, and/or behenic acids and the
diesters of
stearic, oleic, palmitic, lauric, isostearic, behenic, and/or myristic acids.
It is
understood that the typical mono-ester contains some di- and tri-ester, etc.
The "glycerol esters" also include the polyglycerol, e.g., diglycerol through
octaglycerol esters. The polyglycerol polyols are formed by condensing
glycerin or
epichlorohydrin together to link the glycerol moieties via either linkages.
The mono
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and/or diesters of the polyglycerol polyols are preferred, the fatty acyl
groups
typically being those described hereinbefore for the sorbitan and glycerol
esters.
2. Quaternary Ammonium Compound
Compositions of the present invention can contain from 0% to about 20%,
preferably from 0% to about 10%, more preferably from 0% to about 5%, and even
more preferably from about 1% to about 5%, of quaternary ammonium compound,
preferably ester, and/or amide linked.
The quaternary ammonium compounds are typically of the Formulas I, II, and
mixtures thereof.
Formula I comprises:
(R)a-m - ~ -~(CHz)~ - (Y)p - Rz]m X_
wherein
each Y = -0-(0)C-, -N(R)3-C(0)-, -C(0)-N(R)3-, or -C(0)-0-; m = 1 to 3; n = 1
to 4; p = 0 or l; each R substituent is a short chain C,-C6, preferably C,-C3,
alkyl or hydroxy alkyl group, e.g., methyl (most preferred), ethyl,
hydroxyethyl, propyl, and the like, benzyl and mixtures thereof; each Rz is a
long chain, saturated and/or unsaturated (Iodine Value - "IV" of from about 3
to about 60), Cg-C3° hydrocarbyl, or substituted hydrocarbyl
substituent and
mixtures thereof; R3 is R or H; and the counterion, X-, can be any softener-
compatible anion, for example, methylsulfate, ethylsulfate, chloride, bromide,
formate, sulfate, lactate, nitrate and the like, preferably methylsulfate.
It will be understood that substituents R and Rz of Formula I can optionally
be
substituted with various groups such as alkoxyl or hydroxyl groups.
The preferred ester linked compounds (DEQA) can be considered to be diester
variations of ditallow dimethyl ammonium chloride (DTDMAC), which is a widely
used fabric softener. Preferably, at least 80% of the DEQA is in the diester
form, and
from 0% to about 20%, preferably less than about 10%, more preferably less
than
about 5%, can be DEQA monoester (e.g., only one -Y-Rz group). For optimal
antistatic benefit monoester should be low, preferably less than about 2.5%.
The level
of monoester can be controlled in the manufacturing of the DEQA.
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The quaternary softening compounds with at least partially unsaturated alkyl
or acyl groups have advantages (i.e., antistatic benefits) and are highly
acceptable for
consumer products when certain conditions are met. Antistatic effects are
especially
important where the fabrics are dried in a tumble dryer, and/or where
synthetic
S materials which generate static are used. Any reference to IV values
hereinafter refers
to IV of fatty alkyl or acyl groups and not to the resulting quaternary, e.g.,
DEQA
compound. As the IV is raised, there is a potential for odor problems.
For unsaturated softener actives, the optimum storage temperature for
stability
and fluidity depends on the specific IV of, e.g., the fatty acid used to make
DEQA
and/or the level/type of solvent selected. Exposure to oxygen should be
minimized to
keep the unsaturated groups from oxidizing. It can therefore be important to
store the
material under a reduced oxygen atmosphere such as a nitrogen blanket. It is
important to provide good molten storage stability to provide a commercially
feasible
raw material that will not degrade noticeably in the normal
transportation/storage/handling of the material in manufacturing operations.
The following are non-limiting examples of DEQA Formula I (wherein all
long-chain alkyl substituents are straight-chain):
Saturated
[CzHs]z~[CH2CHzOC(0)C"Hss]z SOaCH3_
[C3H,][CZHS] ~N[CHZCHzOC(0)C"H23]2 S04-CH3
[CH3]2 ~ N[CHZCHzOC(0)Rz]2 S04CH3_
where -C(0)RZ is derived from saturated tallow.
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Unsaturated
[CH3J20N[CH2CH20C(0)C17H33J2 S040CH3
[C2H5J2~N[CH2CH20C(0)C17H33J2 C19
[CH2CH20HJ[CH3JoN[CH2CH20C(0)R2]2 CH3S049
[CH3]2oN[CH2CH20C(0)R2J2 CH3S04A
where -C(O)R2 is derived from partially hydrogenated tallow or
modified tallow having the characteristics set forth herein.
In addition to Formula I compounds, the compositions and
articles of the present invention comprise DEQA compounds of
Formula II:
N~(R1)3 - (CH2)n - CH(Q-TI) - CH2(Q-T2) X8
wherein, for any molecule:
each Q is -0-C(0)- or -(0)C-0-;
each R1 is CI-C4 alkyl or hydroxy alkyl;
each TI and T2 is a C8~C30 alkyl or alkenyl group;
n is an integer froa~ 1 to 4; and
XA is a softener-compatible anion; and wherein preferably RI
is a methyl group, n is 1, Q is -0-C(0)-, TI and T2 are
C14-C18~ and Xe is methyl sulfate.
The straight or branched alkyl or alkenyl chains, T1 and T2,
have from about 8 to about 30 carbon atoms, preferably from about
14 to about 18 carbon atoms, more preferably straight chains
having froa~ about 14 to about 18 carbon atoms.
These compounds can be prepared by standard esterification
and quaternization reactions, using readily available starting
materials. General methods for preparation are disclosed in U.S.
Pat. No. 4,137,180.
(3) Qctlonal Soil Release Agent
Optionally, the compositions herein contain from 0% to about
10%, preferably from about 0.1% to about 5%, more preferably from
about 0.1% to about 2%, of a soil release agent. Preferably, such
a soil release agent is a polymer. Polymeric soil release agents
useful in the present invention include copolyaieric blocks of
terephthalate and polyethylene oxide or polypropylene oxide, and
the like. U.S. Pat. No. 4,956,447, Gosselink/Hardy/Trinh, issued
Sept. 11, 1990, discloses specific preferred soil release agents
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comprising cationic functionalities.
A preferred soil release agent is a copolymer having blocks of terephthalate
and polyethylene oxide. More specifically, these polymers are comprised of
repeating
units of ethylene and/or propylene terephthalate and polyethylene oxide
terephthalate
at a molar ratio of ethylene terephthalate units to polyethylene oxide
terephthalate
units of from about 25:75 to about 35:65, said polyethylene oxide
terephthalate
containing polyethylene oxide blocks having molecular weights of from about
300 to
about 2000. The molecular weight of this polymeric soil release agent is in
the range
of from about 5,000 to about 55,000.
U.S. Pat. No. 4,976,879, Maldonado/Trinh/Gosselink, issued Dec. 11, 1990,
discloses specific preferred soil release agents which can also provide
improved
antistatic benefit.
Another preferred polymeric soil release agent is a crystallisable polyester
with repeat units of ethylene terephthalate units containing from about 10% to
about
15% by weight of ethylene terephthalate units together with from about 10% to
about
50% by weight of polyoxyethylene terephthalate units, derived from a
polyoxyethylene glycol of average molecular weight of from about 300 to about
6,000, and the molar ratio of ethylene terephthalate units to polyoxyethylene
terephthalate units in the crystallisable polymeric compound is between 2:1
and 6:1.
Examples of this polymer include the commercially available materials Zelcon~
4780
(from DuPont) and Milease~ T (from ICI).
A more complete disclosure of these highly preferred soil release agents is
contained in European Pat. Application 185,427, Gosselink, published June 25,
1986.
(4) Cyclodextrin/Perfume Complexes and Free Perfume
The products herein can also contain from about 0.5% to about 60%,
preferably from about 1% to about 50%, cyclodextrin/perfume inclusion
complexes,
as disclosed in U.S. Pat. Nos. 5,139,687, Borcher et al., issued August 18,
1992; and
5,234,610, Gardlik et al., to issue Aug. 10, 1993.
Perfumes are highly desirable, can usually benefit from protection, and can be
complexed with cyclodextrin. Fabric softening products typically contain
perfume to
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provide an olfactory aesthetic benefit and/or to serve as a signal that the
product is
effective.
The perfume ingredients and compositions of this invention are the
conventional ones known in the art. Selection of any perfume component, or
amount
of perfume, is based solely on aesthetic considerations. Suitable perfume
compounds
and compositions can be found in the art including U.S. Pat. Nos.: 4,145,184,
Brain
and Cummins, issued Mar. 20, 1979; 4,209,417, Whyte, issued June 24, 1980;
4,515,705, Moeddel, issued May 7, 1985; and 4,152,272, Young, issued May 1,
1979.
Many of the art recognized perfume compositions are relatively substantive,
as described hereinafter, to maximize their odor effect on substrates.
However, it is a
special advantage of perfume delivery via the perfume/cyclodextrin complexes
that
nonsubstantive perfumes are also effective. The volatility and substantivity
of
perfumes is disclosed in U.S. Pat. No. 5,234,610, supra.
If a product contains both free and complexed perfume, the escaped perfume
from the complex contributes to the overall perfume odor intensity, giving
rise to a
longer lasting perfume odor impression.
As disclosed in U.S. Pat. No. 5,234,610, supra, by adjusting the levels of
free
perfume and perfume/CD complex it is possible to provide a wide range of
unique
perfume profiles in terms of timing (release) and/or perfume identity
(character).
Solid, dryer-activated fabric conditioning compositions are a uniquely
desirable way
to apply the cyclodextrins, since they are applied at the very end of a fabric
treatment
regimen when the fabric is clean and when there are almost no additional
treatments
that can remove the cyclodextrin.
(5) Stabilizers
Stabilizers can be present in the compositions of the present invention. The
term "stabilizer", as used herein, includes antioxidants and reductive agents.
These
agents are present at a level of from 0% to about 2%, preferably from about
0.01 % to
about 0.2%, more preferably from about 0.05% to about 0.1% for antioxidants
and
more preferably from about 0.01 % to about 0.2% for reductive agents. These
assure
good odor stability under long term storage conditions for the compositions.
Use of
CA 02168975 2000-10-03
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antioxidants and reductive agent stabilizers is especially critical for
unscented or low
scent products (no or low perfume).
Examples of antioxidants that can be added to the compositions of this
invention include ascorbic acid, ascorbic palmitate, propyl gallate, available
from
Eastman Chemical Products, Inc., under the trade names Tenox~ PG and Tenox S-
1;
a mixture of BHT, BHA, propyl gallate, and citric acid, available from Eastman
Chemical Products, Inc., under the trade name Tenox-6; butylated
hydroxytoluene,
available from UOP Process Division under the trade name Sustane~ BHT;
tertiary
butylhydroquinone, Eastman Chemical Products, Inc., as Tenox TBHQ; natural
tocopherols, Eastman Chemical Products, Inc., as Tenox GT-1/GT-2; and
butylated
hydroxyanisole, Eastman Chemical Products, Inc., as BHA.
Examples of reductive agents include sodium, borohydride, hypophosphorous
acid, and mixtures thereof.
The stability of the compounds and compositions herein can be helped by the
stabilizers, but in addition, the preparation of compounds used herein and the
source
of hydrophobic groups can be important. Surprisingly, some highly desirable,
readily
available sources of hydrophobic groups such as fatty acids from, e.g.,
tallow, possess
odors that remain with the compound, e.g., DEQA despite the chemical and
mechanical processing steps which convert the raw tallow to finished DEQA.
Such
sources must be deodorized, e.g., by absorption, distillation (including
stripping such
as steam stripping), etc., as is well known in the art. In addition, care must
be taken
to minimize contact of the resulting fatty acyl
2~ ~897~
- 16 -
groups to oxygen and/or bacteria by adding antioxidants, anti-
bacterial agents, etc. The additional expense and effort asso-
ciated with the unsaturated fatty acyl groups is justified by the
superior performance which has not been recognized.
(6) Other Optional Inaredi ~t~
The present invention can include other optional components
(minor components) conventionally used in textile treatment
compositions, for example, colorants, preservatives, optical
brighteners, opacifiers, physical stabilizers such as guar gum and
10 polyethylene glycol, anti-shrinkage agents, anti-wrinkle agents,
fabric crisping agents, spotting agents, germicides, fungicides,
anti-corrosion agents, antifoam agents, and the like.
(0) Substrate Articles
In preferred embodiments, the present invention encompasses
15 articles of manufacture. Representative articles are those that
are adapted to soften fabrics in an automatic laundry dryer, of
the types disclosed in U.S. Pat. Nos.: 3,989,631 Marsan, issued
Nov. 2, 1976; 4,055,248, Marsan, issued Oct. 25, 1977; 4,073,996,
Bedenk et al., issued Feb. 14, 1978; 4,022,938, Zaki et al.,
20 issued May 10, 1977; 4,764,289, Trinh, issued Aug. 16, 1988;
4,808,086, Evans et al., issued Feb. 28,1989; 4,103,047, Zaki et
al., issued July 25, 1978; 3,736,668, Oillarstone, issued June 5,
1973; 3,701,202, Compa et al., issued Oct. 31,1972; 3,634,947,
Furgal, issued Jan. 18, 1972; 3,633,538, Hoeflin, issued Jan. 11,
25 1972; and 3,435,537, Russey, issued Apr. 1, 1969; and 4,000,340,
Murphy et al., issued Dec. 28, 1976.
In a preferred substrate article embodiment, the fabric
treatment compositions are provided as an article of manufacture
30 in combination with a dispensing means such as a flexible sub-
strate which effectively releases the composition in an automatic
laundry (clothes) dryer. Such dispensing means can be designed
for single usage or for multiple uses. The dispensing means can
also be a "carrier material" that releases the fabric softener
35 composition and then is dispersed and/or exhausted from the dryer.
2168975
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The dispensing means will normally carry an effective amount
of fabric treatment composition. Such effective amount typically
provides sufficient fabric conditioning/antistatic agent and/or
anionic polymeric soil release agent for at least one treatment of
a minimum load in an automatic laundry dryer. Amounts of fabric
treatment composition for multiple uses, e.g., up to about 30, can
be used. Typical amounts for a single article can vary from about
0.25 g to about 100 g, preferably from about 0.5 g to about 20 g,
most preferably from about 1 g to about 10 g.
Highly preferred paper, woven or nonwoven 'absorbent' sub-
strates useful herein are fully disclosed in U.S. Pat. No.
3,686,025, Morton, issued Aug. 22, 1972.
It is known that most substances are able to absorb a
liquid substance to some degree; however, the terra 'absorbent' as
used herein, is intended to mean a substance with an absorbent
capacity (i.e., a parameter representing a substrate's ability to
take up and retain a liquid) from 4 to 12, preferably 5 to 7,
times its weight of water.
Another article comprises a sponge material releasably
enclosing enough fabric treatment composition to effectively
impart fabric soil release, antistatic effect and/or softness
benefits during several cycles of clothes. This mufti-use article
can be made by filling a hollow sponge with about ,20 grams of the
fabric treatment composition.
(E) Usace
The substrate embodiment of this invention can be used for
imparting the above-described fabric treatment composition to
fabric to provide softening and/or antistatic effects to fabric in
an automatic laundry dryer. Generally, the method of using the
composition of the present invention comprises: commingling pieces
of damp fabric by tumbling said fabric under heat in an automatic
clothes dryer with an effective amount of the fabric treatment
composition. At least the continuous phase of said composition
has a melting point greater than about 35'C and the composition is
CA 02168975 2000-10-03
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flowable at dryer operating temperature. This composition comprises from about
5%
to about 90%, preferably from about 10% to about 75%, of the ethoxylated sugar
derivative and from about 10% to about 95%, preferably from about 20% to about
75%, more preferably from about 20% to about 60% of the above-defined co-
softeners.
The present invention relates to improved solid dryer-activated fabric
softener
compositions which are either (A) incorporated into articles of manufacture in
which
the compositions are, e.g., on a substrate, or are (B) in the form of
particles
(including, where appropriate, agglomerates, pellets, and tablet of said
particles).
All percentages, ratios, and parts herein, in the Specification, Examples and
Claims, are by weight and approximations unless other stated.
The following are nonlimiting examples of the instant articles, methods, and
compositions of the present invention.
~v n r.rnr ~ ~
Components Wt.%
Co-softener* 27.21
Glycosperse S-20 17.44
Perfume/Cyclodextrin Complex 16.04
Clay** 3.14
Free Perfume 1.29
Sobitan Monostearate 34.88
100.0
Glycosperse S-20 is polyethoxylated sorbitan monostearate, from Lonza,
which contains about 20 ethoxylate moieties per molecule.
* 1:2 ratio of stearyldimethylamineariple-pressed stearic acid.
**Calcium bentonite clay, Bentolite L, sold by Southern Clay Products, or
Gelwhite
GP clay.
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PREPARATION OF THE COATING MIX
An approximately 200g batch of the coating mix is prepared as follows. An
amount of about 54g of co-softener and about 70g of sorbitan monostearate
(SMS)
are melted separately at about 80°C. Separately, about 35g of
Glycosperse S-20 is
also melted at about 80°C. The co-softener/SMS blend and Glycosperse S-
20 are then
combined with high shear mixing. During the mixing, the mixture is kept molten
in a
hot water bath at about 70-80°C. The complex (about 32g) is ground and
slowly
added to the mixture with high shear mixing. The calcium bentonite clay (about
6g)
is slowly added to the mixture with high shear mixing until the desired
viscosity is
achieved. The perfume (about 3g) is added to the mixture, and the formula is
mixed
until the mixture is smooth and homogeneous.
PREPARATION OF FABRIC CONDITIONING SHEETS
The coating mixture is applied to preweighed substrate sheets of about 6.75
inches x 12 inches (approximately 17 cm x 30 cm) dimensions. The substrate
sheets
are comprised of about 4-denier spun bonded polyester. A small amount of the
formula is placed on a heated metal plate with a spatula and then is spread
evenly
with a wire metal rod. A substrate sheet is placed on the metal plate to
absorb the
coating mixture. The sheet is then removed from the heated metal plate and
allowed
to cool to room temperature so that the coating mix can solidify. The sheet is
weighed to determine the amount of coating mixture on the sheet. The target
sheet
weight is 3.38g. If the weight is in excess of the target weight, the sheet is
placed
back on the heated metal plate to remelt the coating mixture and remove some
of the
excess. If the weight is under the target weight, the sheet is also placed on
the heated
metal plate and more coating mixture is added.
EXAMPLE 2
The coating mix preparation and the making of the fabric conditioning sheets
are similar to those in Example 1, except that Glycosperse S-5 is used instead
of
Glycosperse S-20.
CA 02168975 2000-10-03
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r, v ~ a mr r. ~
The coating mix preparation and the making of the fabric conditioning sheets
are similar to those in Example 1, except that Glycosperse S-10 is used
instead of
Glycosperse S-20.
EXAMPLE 4
Components Wt.%
Co-softener* 43.15
Glycosperse S-20 49.84
Clay** 5.39
Free Perfume 1.62
100.0
*1:2 ratio of stearyldimethylamineariple-pressed stearic acid.
**Calcium bentonite clay, Bentolite L, sold by Southern Clay Products, or
Gelwhite GP clay.
The coating mix preparation and the making of the fabric conditioning sheets
are similar to those in Example 1, except that the target sheet weight is
2.85g.
EXAMPLE 5
The coating mix preparation and the making of the fabric conditioning sheets
are similar to those in Example 4, except that Glycosperse S-15 is used
instead of
Glycosperse S-20.
T~7 ~ 1 TT T
Components Wt.%
Glycosperse S-20 94.59
Clay** 5.41
100.0
**Calcium bentonite clay, Bentolite L, sold by Southern Clay Products, or
Gelwhite GP clay
The coating mix preparation and the making of the fabric conditioning sheets
are similar to those in Example 1.
CA 02168975 2000-10-03
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EXAMPLE 7
The coating mix preparation and the making of the fabric conditioning sheets
are similar to those in Example 1, except that the co-softener is a 1:2 ratio
of
oleyldimethylamine to triple-pressed stearic acid instead of
stearyldimethylamine and
triple-pressed stearic acid.
EXAMPLE 8
Components Wt.%
Co-softener* 27.21
Sorbitan Monostearate 17.44
Glycosperse S-20 17.44
Perfume/Cyclodextrin Complex 16.04
Clay** 3.14
Free Perfume 1.29
Dimethyl Bis(oleyloxyethyl)
Ammonium Methyl Sulfate 17.44
100.0
Glycosperse S-20 is polyethoxylated sorbitan monostearate, from Lonza,
which contains about 20 ethoxylate moieties per molecule.
* 1:2 ratio of stearyldimethylamineariple-pressed stearic acid.
**Calcium bentonite clay, Bentolite L, sold by Southern Clay Products, or
Gelwhite GP clay
The coating mix preparation and the making of the fabric conditioning sheets
are similar to those in Example 1.
